Silicone containing automotive vinyl protectant

ABSTRACT

A method is described for providing a protective finish to a vinyl substrate by applying to the vinyl substrate a vinyl protectant composition. In one embodiment the composition is an abrasive free mixture of a film forming polysiloxane; a diluent; and a wax in the form of micronized particles having an average diameter of 3-12 microns. In another embodiment, the composition is a hydrocarbon solvent free mixture of a film forming polysiloxane; water; and an amorphous silica in the form of fumed silica particles having an average diameter of 7-30 nanometers.

BACKGROUND OF THE INVENTION

The invention relates to a vinyl protectant formulation containingmicronized wax particles which have been found to reduce the glare ofapplied films. The invention also relates to vinyl protectantformulations containing fumed silica particles which not only reduce theglare of applied films but decrease the oily appearance and feel of suchconsumer applied products.

While leather is the material of choice, leatherlike materials arefinding widespread use as substitutes for leather in applications whereleather has been used traditionally. Synthetic leatherlike materials areless expensive substitutes for leather, and therefore in seating,upholstery and interior trim, leatherlike materials in the form ofcoated fabrics are prevalent in the automotive market where lower pricesprovide a competitive advantage. The most important polymer used incoated fabrics is polyvinyl chloride. This relatively inexpensivepolymer resists aging processes readily, resists burning, and is verydurable, rendering it ideal for vehicle upholstery and interior trim.

Many vinyl protectant products for cleaning, preserving and conditioningvinyl surfaces are formulated with the express purpose of providing ahigh level of gloss to the surface to which they are applied. However,automobile designs have changed and some models feature steeply slopingwindshields. Because of the steepness of slope of the windshield, it hasbeen found that glossy dashboards produce a glare on the windshieldglass which creates a potential safety hazard for the driver of thevehicle. In an effort to solve the problem, some manufacturers havedesigned dashboard materials with a lower gloss level, and vehicleowners' manuals contain warnings against the use of consumer appliedproducts which would tend to increase the level of gloss of thedashboard.

This trend toward softer-looking interiors has created the need for newvinyl protectant formulations which provide a reduced level of glare onsurfaces to which they are applied. In accordance with the presentinvention, certain particulate materials when added to vinyl protectantformulations have been found to function as flattening agents and causea significant decrease in glare, and in an alternate embodiment certainparticulate materials provide an added benefit of simultaneously causinga reduction in the oily appearance and feel often characteristic of suchproducts.

SUMMARY OF THE INVENTION

This invention is directed to a method for providing a protective finishto a vinyl substrate by the application to the vinyl substrate of acertain vinyl protectant formulation. In one embodiment of theinvention, the formulation is an abrasive free mixture of a film formingpolysiloxane; a diluent; and a wax in the form of micronized particleshaving an average diameter of 3-12 microns. Unexpectedly, it has beendiscovered that the micronized wax particles perform a beneficialfunction in reducing the gloss of the vinyl protectant as applied. Thisis a significant advantage in meeting the need of consumer appliedautomotive products which demand low glare capability especially as itrelates to vehicle dashboard surfaces and interior trim.

In another and alternate embodiment of the present invention, theformulation constitutes a hydrocarbon solvent free mixture of a filmforming polysiloxane; water; and an amorphous silica in the form offumed silica particles having an average diameter of 7-30 nanometers.Like the first embodiment, unexpectedly it has been discovered that thesilica particles reduce the gloss of the vinyl protectant as applied. Inaddition, the typical oily appearance and feel of consumer appliedautomotive vinyl protectant products is reduced with formulations inaccordance with this alternate embodiment.

These and other features, objects and advantages of the presentinvention will become more apparent from a consideration of thefollowing detailed description thereof.

DETAILED DESCRIPTION OF THE INVENTION

The silicone component of the vinyl protectant formulations of thepresent invention is an organic polysiloxane which is a film formerhaving a viscosity in the range of about 5 to as high as several millioncentistokes, preferably about 100 to about 10,000 centistokes. Morepreferably, a mixture of polysiloxanes having relatively higher andrelatively lower viscosities can be employed. Such polysiloxanes havethe repeating unit ##STR1## wherein n is an integer having a valuegreater than 1, R¹ is an alkyl radical containing 1 to 7 carbon atoms,inclusive, or a phenyl group, R² is hydrogen, an alkyl radicalcontaining 1 to 7 carbon atoms, inclusive, or a phenyl group.Illustrative polysiloxanes encompassed by the above formula arepolydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane,polymethylphenylsiloxane, polydiphenylsiloxanes, diphenylsilanediol, andcopolymers of two or more of the foregoing siloxanes.Polysiloxaneoxyalkylene block copolymers and silicone resins may also beutilized. Where the polysiloxane film former selected is a siliconeresin, it is preferred in accordance with the present invention toemploy a silanol functional phenyl based silicone resin having presentin the resin CH₃ SiO₁.5, (CH₃)₂ SiO, (CH₃)(C₆ H₅)SiO, and (C₆ H₅)₂ SiOsiloxane units. Such resins are typically commercially available in theform of a hydrocarbon solvent containing about fifty percent by weightsolids.

In addition to the aforementioned organic polysiloxanes, the presentcompositions may include an aminofunctional polysiloxane. Theamino-functional polysiloxane is a silicone fluid with highly polarpendant aminoalkyl modifying groups that enhance the durability of thefilm formed by the polysiloxanes present and promotes adhesion of theformed film to the vinyl substrate. Particularly preferredaminofunctional polysiloxanes include reactive and non-reactivehydrolyzable and non-hydrolyzable derivatives which are wholly, or inpart, terminally substituted with aminopropyl, aminobutyl, or diaminopendant chains. Amine functional siloxane polymers can be represented bythe formula

    R.sub.3-z 'Q.sub.z SiO[R.sub.2 'SiO].sub.x [R'QSiO].sub.y SiQ.sub.z R.sub.3-z '

wherein R' denotes an alkyl group of 1 to 4 carbons, OH, an alkoxygroup, or a phenyl group, with the proviso that at least 50 percent ofthe total R' groups are methyl; Q denotes an amine functionalsubstituent of the formula --R"Z in which R" is a divalent alkyleneradical of 3 to 6 carbon atoms or a radical of the formula --CH₂ CH₂ CH₂OCH₂ CHOHCH₂ -- and Z is a monovalent radical selected from the groupconsisting of --NR₂ '", --NR'"(CH₂)_(n) NR₂ '"; and ##STR2## wherein R'"denotes hydrogen or an alkyl group of 1 to 4 carbons, R"" denotes analkyl group of 1 to 4 carbons and n is a positive integer from 2 to 6; zhas a value of 0 or 1; x has an average value of 25 to 3000; y has anaverage value of 0 to 100 when z is 1, y has an average value of 1 to100 when z is 0; with the proviso that in all cases y has an averagevalue that is not greater than one tenth the average value of x.

The vinyl protectants may include volatile low viscosity silicone fluidssuch as polydimethylcyclosiloxane and hexamethyldisiloxane. Such fluidshave viscosities measured at twenty-five degrees Centigrade of fromabout 0.65 to about 5.0 centistokes. These volatile silicone fluids havethe formula (CH₃)₂ SiO_(x) in which x is an integer from three to eight,and are often in the form of mixtures of tetramers and pentamers.

The silicone component of the vinyl protectant formulations of thepresent invention as enumerated above are commercially availablematerials known in the art.

The wax component of the vinyl protectant formulation of one embodimentof the present invention is a micronized particle form of one or moreotherwise conventional waxes such as Fisher-Tropsch wax, polyethylenewax, polyethylene-polytetrafluoroethylene wax, polytetrafluoroethylenewax, polypropylene wax, natural wax, mineral wax, montan waxderivatives, fatty acid wax derivatives, amide wax, and mixturesthereof. While the particle size of these micronized wax particlestypically varies from an average diameter of 2-45 microns, particlesizes in the range of 3-12 microns are preferred in the formulations inaccordance with the present invention. Micronized wax particles areknown in the art as evidenced by U.S. Pat. No. 4,846,887 issued Jul. 11,1989. Micronized wax particles most suitable for use in the presentinvention are available from Micro Powders, Incorporated, Tarrytown,N.Y., and are sold under the trademark AQUABEAD®. AQUABEAD® products270E, 418E and 519 are particularly preferred. These products areavailable in the form of aqueous wax emulsions having a viscosity of35-500 centistokes and containing various combinations of paraffin andpolyolefin waxes.

Diluents suitable for use in formulating products in accordance with thepresent invention are water, toluene, mineral spirits, ethanol andisopropanol.

The silica component of the vinyl protectant formulation of an alternateembodiment of the present invention is an amorphous silica particle.Preferably, the amorphous silica is in the form of fumed silicasometimes referred to as pyrogenic silica, although other forms ofamorphous silica including naturally occurring amorphous silica could beemployed. The critical feature however is that the particle size of theamorphous silica used be in the range of 7-30 nanometers, in order toachieve the benifits and advantages of the present invention. Theamorphous silica found to be most suitable for purposes of the presentinvention is a colloidal form of silica particle having a surface areaof 175-225 square meters per gram, and which is available commerciallyfrom Cabot Corporation, Tuscola, Ill. under the trademark Cab-O-Sil®M-5.

The concept of the invention is present in the form of two alternateembodiments. In the first embodiment, there is provided a method ofproviding a protective finish to a vinyl substrate in which there isapplied to the vinyl substrate a vinyl protectant formulation which isan abrasive free mixture of 5-60 percent by weight of a film formingpolysiloxane; 20-50 percent by weight of a diluent; and 1-20 percent byweight of a wax in the form of micronized particles having an averagediameter of 3-12 microns. While various polysiloxanes may be used as thefilm former as enumerated above, preferably the film formingpolysiloxane is a polydimethylsiloxane fluid having a viscosity of 100to 1,000 centistokes, most preferably about 350 centistokes, or asilicone resin such as a silanol functional phenyl based silicone resinhaving present in the resin CH₃ SiO₁.5, (CH₃)₂ SiO, (CH₃)(C₆ H₅)SiO, and(C₆ H₅)₂ SiO siloxane units. The diluent for the first embodiment may beone of water, toluene, mineral spirits, ethanol or isopropanol.

According to a second or alternate embodiment of the present invention,there is set forth a method of providing a protective finish to a vinylsubstrate by applying to the vinyl substrate a vinyl protectantformulation which is a hydrocarbon solvent free mixture of 5-60 percentby weight of a film forming polysiloxane; 20-50 percent by weight ofwater; and 0.25-5 percent by weight of an amorphous silica in the formof fumed silica particles having an average diameter of 7-30 nanometers.The film forming polysiloxane used in the second embodiment can be thesame as the polysiloxane used in the first embodiment noted above. Mostpreferably, the film forming polysiloxane is present in the mixture inan amount of 10-35 percent by weight, and the amorphous silica ispresent in the mixture in an amount of 0.25-2.5 percent by weight.

The following examples are set forth for the purpose of illustratingboth the first and second embodiments of the present invention.

EXAMPLE I

In order to show the use and function of micronized wax particles as amatting agent in silicone containing vinyl protectant formulations,several abrasive free vinyl treating formulations were prepared and theconstituents of each formulation are shown in Table I. The film formingpolysiloxane employed in this example was a silicone resin in toluenediluted to a solids content of twenty percent by weight. The siliconeresin was a silanol functional phenyl based silicone resin having CH₃SiO₁.5, (CH₃)₂ SiO, (CH₃)(C₆ H₅)SiO, and (C₆ H₅)₂ SiO siloxane units.The wax component of the abrasive free vinyl treating formulation was inthe form of a micronized wax particle having an average diameter in therange of 3-12 microns. The micronized wax particle is commerciallyavailable from Micro Powders, Incorporated, Tarrytown, N.Y., under thetrademark AQUABEAD® 519. The micronized wax particle was employed in thevarious formulations at a content which varied from a zero percentcontrol formulation, to a formulation containing six weight percent ofthe micronized wax particle based on the weight of the activeingredients.

                  TABLE I                                                         ______________________________________                                                 Silicone     Toluene                                                          Film Former  Diluent  Micronized Wax                                 Formulation                                                                            (grams)      (grams)  (grams)                                        ______________________________________                                        A        18.0         27.22    --                                             B        18.0         26.10    0.90                                           C        18.02        25.21    1.80                                           D        18.02        24.32    2.71                                           ______________________________________                                    

Formulations A-D were each hand applied to a separate section of a grayautomotive vinyl material. Following the elapse of thirty minutes, eachgray vinyl test piece was visually examined under standard laboratorylighting. Each of the formulations was observed to have provided anoticeable enrichment in the color of the gray vinyl test piece. Inparticular, formulations B, C and D which contained the micronized waxparticles were observed to have provided the added and unexpectedbenefit of a satiny lower gloss overall appearance. The lower glossappearance of formulations B-D indicated that the micronized waxparticles were capable of functioning as a matting agent in an abrasivefree silicone containing vinyl protectant formulation. This function ofthe micronized wax particles is an advantage and benefit in formulatingreduced glare products for meeting current demands of "softer looking"interiors for the automotive cleaner and coating market.

EXAMPLE II

Example I was repeated except that the film forming polysiloxaneemployed was a polydimethylsiloxane fluid having a viscosity of 350centistokes measured at twenty-five degrees Centigrade which was dilutedin mineral spirits to a content of twenty percent by weight. Theformulations are shown below in Table II and the evaluations of theseformulations was the same as the evaluations of Example I.

                  TABLE II                                                        ______________________________________                                                 Silicone     Toluene                                                          Film Former  Diluent  Micronized Wax                                 Formulation                                                                            (grams)      (grams)  (grams)                                        ______________________________________                                        A        4.00         16.00    --                                             B        4.00         15.71    0.50                                           C        4.00         15.31    0.80                                           D        4.01         14.80    1.20                                           ______________________________________                                    

EXAMPLE III

Example I was repeated except that the film forming polysiloxaneemployed was a sixty percent solids aqueous emulsion ofpolydimethylsiloxane fluid having a viscosity of 350 centistokes whichhad been emulsified using a nonionic surfactant. The wax component was amicronized wax particle available from Micro Powders, Incorporated,Tarrytown, N.Y., under the trademark AQUABEAD® 418E which is similar toAQUABEAD® 519 of Example I except that AQUABEAD® 418E is in the form ofa specific thirty-five percent wax solids aqueous emulsion. Theformulations were produced by shaking together the two emulsions. Noother diluent was used to prepare these formulations. The formulationsare shown below in Table III and the evaluations of these formulationswas the same as the evaluations of Examples I and II, except that inExample III the formulations D and E exhibited significantly less glossthan the control formulation A while producing a satiny finish whichenriched the color of the vinyl test piece.

                  TABLE III                                                       ______________________________________                                                 Silicone                                                                      Film Former                                                                              Wax Weight  Micronized Wax                                Formulation                                                                            (grams)    Percent     (grams)                                       ______________________________________                                        A        16.00      --          --                                            B        16.53      2           1.00                                          C        15.54      4           2.00                                          D        14.53      6           3.03                                          E        11.50      12          6.00                                          ______________________________________                                    

EXAMPLE IV

Example III was repeated except that the film forming polysiloxaneemployed was a twenty-five percent solids aqueous emulsion ofpolydimethylsiloxane fluid in the form of a leading commerciallyavailable vinyl protectant. Two wax components were used each of whichwas a micronized wax particle available from Micro Powders,Incorporated, Tarrytown, N.Y., under the trademark AQUABEAD® 418E asnoted in Example III and a second micronized wax particle AQUABEAD®270E. AQUABEAD® 270E is the same as AQUABEAD® 418E with the exception ofthe particular paraffin and polyolefin waxes used to make the product.The formulations were produced by shaking together the three emulsions.No other diluent was used to prepare these formulations. Theformulations containing ten and twenty weight percent of the micronizedwax particles are shown below in Table IV. The formulations were appliedto gray automotive vinyl and the following day gloss measurements weretaken.

                  TABLE IV                                                        ______________________________________                                               Silicone   AQUABEAD ®                                                                              AQUABEAD ®                                Formula-                                                                             Film Former                                                                              418E Wax      270E Micronized                               tion   (grams)    (grams)       Wax (grams)                                   ______________________________________                                        A      20.07      2.07          --                                            B      20.02      --            2.00                                          C      20.07      4.02          --                                            D      20.24      --            4.14                                          E      20.00      --            --                                            ______________________________________                                    

Gloss was measured at an angle of sixty degrees with a GardnerGlossmeter. The instrument was calibrated with standards and threereadings were taken for each of the samples tested. An average and astandard deviation were calculated for each sample. Comparisons weremade with control samples. The results are set forth below in Table Vand indicate that the formulations containing the micronized waxparticles provided a reduction in gloss.

                  TABLE V                                                         ______________________________________                                                              +/-       Percent                                       Formulation                                                                              Gloss      Deviation Reduction                                     ______________________________________                                        A          6.7        .31       15.2                                          B          7.0        .26       11.4                                          C          5.9        .16       25.3                                          D          6.1        .16       22.8                                          E          7.9        .42       --                                            Blank Gray 3.3        .05       --                                            Vinyl Test                                                                    Surface                                                                       ______________________________________                                    

EXAMPLE V

To illustrate the second and alternate embodiment of the presentinvention, amorphous silica with a particle size in the range of 7-30nanometers was used to prepare an organic solvent free vinyl protectantformulation. The amorphous silica was a colloidal form of silicaparticle having a surface area of 175-225 square meters per gramavailable from Cabot Corporation, Tuscola, Ill. under the trademarkCab-O-Sil® M-5. The fumed silica was added to a twenty-five percentsolids aqueous emulsion of polydimethylsiloxane fluid in the form of aleading commercially available vinyl protectant. The fumed silicacomponent was present in the test formulations at a level of from0.25-2.5 weight percent. The test formulations are shown below in TableVI.

                  TABLE VI                                                        ______________________________________                                                       Silicone   Fumed                                                              Film Former                                                                              Silica                                              Formulation    (grams)    (grams)                                             ______________________________________                                        A              20.04      0.50                                                B              20.23      0.21                                                C              20.38      0.10                                                D              20.17      0.05                                                Control        20.00      --                                                  ______________________________________                                    

Each of the formulations was applied to blue automotive vinyl. Visualexaminations were conducted under both laboratory lighting and outdoorsin the sunlight. It was observed that an increase of the level of silicain the formulation caused a decrease in both the gloss of theformulation as well as a decrease in the oiliness of the formulation. Inparticular, formulation A which contained 2.5 percent silica produced anon-oily matte finish on the vinyl test piece. Sample B produced afinish on the vinyl test piece which retained the gloss level incomparison to the control formulation but which reduced the oilyappearance and feel of the control formulation, which in this examplewas a leading commercially available vinyl protectant. This glossreduction and the combined reduction of oiliness is an unexpectedbenefit and advantage of the formulations in accordance with thisembodiment of the present invention.

It will be apparent from the foregoing that many other variations andmodifications may be made in the compounds, compositions and methodsdescribed herein without departing substantially from the essentialfeatures and concepts of the present invention. Accordingly, it shouldbe clearly understood that the forms of the invention described hereinare exemplary only and are not intended as limitations on the scope ofthe present invention as defined in the appended claims.

That which is claimed is:
 1. A method of providing a protective finishto a vinyl substrate comprising applying to the vinyl substrate a vinylprotectant composition which is an abrasive free mixture of 5-60 percentby weight of a film forming polysiloxane which is selected from thegroup consisting of a polydimethylsiloxane having a viscosity of 100 to1000 centistokes and having a silanol functional phenyl based siliconeresin having present in the resin CH₃ SiO₁.5, (CH₃)₂ SiO, (CH₃)(C₆H₅)SiO, and (C₆ H₅)₂ SiO siloxane units; 20-50 percent by weight of adiluent; and 1-20 percent by weight of a wax in the form of micronizedparticles having an average particle size of 3-12 microns.
 2. A methodaccording to claim 1 in which the diluent is selected from the groupconsisting of water, toluene, mineral spirits, ethanol and isopropanol.3. A method of providing a protective finish to a vinyl substratecomprising applying to the vinyl substrate a vinyl protectantcomposition which is a hydrocarbon solvent free mixture of 5-60 percentby weight of a film forming polysiloxane which is selected from thegroup consisting of a polydimethylsiloxane fluid having a viscosity of100 to 1000 centistokes and having a silanol functional phenyl basedsilicone resin having present in the resin CH₃ SiO₁.5, (CH₃)₂ SiO,(CH₃)(C₆ H₅)SiO, and (C₆ H₅)₂ SiO siloxane units; 20-50 percent byweight of water; and 0.25-5 percent by weight of an amorphous silica inthe form of fumed silica particles having an average particle size of7-30 nanometers.
 4. A method according to claim 3 in which the filmforming polysiloxane is present in the mixture in an amount of 10-35percent by weight.
 5. A method of providing a protective finish to avinyl substrate comprising applying to the vinyl substrate a vinylprotectant composition which is a hydrocarbon solvent free mixture of5-60 percent by weight of a film forming polysiloxane; 20-50 percent byweight of water; and 0.25-2.5 percent by weight of an amorphous silicain the form of fumed silica particles having an average particle size of7-30 nanometers.